Sulfonated detergent and its method of preparation



July 26, A. LEWIS SgULEOIIA'I'ED DETERGENT AND ITS METHOD OF PREPARATIONFiled Dec. 26, 1946 4 Sheets-Sheet 1 PROPYLENE I I CA TALVT/C tPOLYMERIZA TION OLEOFINES BOILING FRAGTIONATION BELOW 300 F aorrousBOILING I ABOVE 500; A crcuc OLEFINE (80/7/09 w/M/n 300"- 600 BENZE NE kY CATALYST ALKVLAT/ON F M l BENZENE FRACTIONA r/o/v I '01- A 1.1m.

. BENZENES ;MONO-PHENYL ALKANES v (Ea/ling mmm 370-600F) SULFQNAT/NGAGE/v1 Y SULFONA TION Ac'm LA YER Na 0H p I SOLUTION v NEUTRAL/2A TION/N VE N TORS DETERGENT PRODUCT 632%- July 26, 1949. A. H. LEWIS2,477,383

SULFONATED DETERGENT AND ITS METHOD OF PREPARATION July 26, 1949. A. H.LEWIS 2,477,383

SULFONATED DETERGENT AND ITS METHOD OF PREPARATION Filed Dec. 26, 1946 4Sheets-Sheet 3 //V VE/V 70/95 A060 L ew/j A TTU/Q/VEKY A. H. LEWIS July26, 1949.

SULFONATED DETERGENT AND ITS METHOD OF PREPARATION Filed Dec. 26, 1946 4Sheets-Sheet 4 INVENTOAS Allen H Lew/Is ATTORNEY-5 Plane: July 26, 1949SULFONATED DETERGENT AND ITS METHOD OF PREPARATION Allen H. Lewis,Berkeley, Caiii'., assignor to Cali-- tornia Research Corporation, SanFrancisco, Calif., a corporation of Delaware Application December 26,1946, Serial No. 718,492

25 Claims. (Cl. 252-161) This invention relates to a novel mixture ofnew phenyl-substituted alkanes and sulfonated derivatives thereof. Moreparticularly the invention is concerned with the production of suchcompounds in which the alkane portion of the molecule is of relativelyhigh molecular weight and preferably contains from about 12 to about 15carbon atoms.

In the production of sulfonate detergents and particularly theirrelatively high molecular weight phenyl alkane components by alkylation.or condensation reactions, a paramount problem has been the provisionof a suitable alkane. Olefins such as butene polymers have been proposedas an alkane source, but introduce outstanding difilculties which arisefrom instability of the branched-aliphatic chains characteristic of suchpolymers. Straight-chain olefins are of limited availability andprohibitive in cost. The

instability of branched aliphatic polymer chains is reflected, forexample, in alkylating and condensation reactions withbenzene or tolueneand results in degradation of the polymer chain during condensation.

This degradation leads to the production of a mixture of phenyl alkanescontaining compounds both lower and higher in aliphatic molecular weightthan the olefin originally selected and desired. The instability andd88- radation of the oleflnpolymers in the presence of condensationcatalysts under alkylating conditions also leads to theproduction ofsubstantially inseparable polyalkylated aromatics of the same molecularweight and boiling range as the desired phenyl alkanes. This is adecided disadvantage since, upon conversion of suchdegraded mixtures tothe sulfonated phenyl derivatives, relatively low yields have resulted;

The sulfonated derivatives tend to be relatively poor in detergentquality and require costly purification treatment to eliminate or reduceodor, unsulfonatable residua, color bodies, and other impuritiesintroduced by degradation caused by the original instability of theolefin polymer. Heretofore such deficiencies have seemed to be inherentin the branched-chain structure of olefin polymers, and the mixture ofphenyl alkanes derived from such polymers have contained relativelylargequantities of polyalkylated aromatics 2 and unsulfonatable residua. Atbest these impurities have not been entirely separable and have impartedundesirable odor or color to the sulfonated products.

An object of this invention is to produce an improved mixture ofsulfonated phenyl substituted branched-chain alkanes of relatively highmolecular weight and excellent detergency.

A further object is the production of a mixture of phenyl alkanes havinga low unsulfonatable residue and a branched-chain structure.

Additionally an object of the invention is to furnish phenyl alkanesconvertible to sulfonatedphenyl alkane detergents of good color andhaving an exceptionally low content of deleterious degradation productsor impurities.

' Another object of the invention is to provide a novel mixture ofphenyl sulfonate substituted alkanes having valuable detergentproperties.

A further object is to produce an improved detergent comprisingvamixture of phenyl alkane sulfonates of improved color and odor. I

Other objects and advantages of the invention will become apparent fromthe following description and the drawings in which:

Figure 1 is a flow sheet illustrating in block diagram the majorfeatures and process steps for the production of a mixture of phenylalkanes and conversion thereof to a phenyl-sulfonate substituted alkanemixture in accordance with the invention.

Figure 2, 3 and 4 when taken together and laid side by side from left toright in their respective order, show in diagrammatic form a processwith the principal units of apparatus for con,- version of propylene andbenzene to an eflfective detergent.

polymerization catalyst. Propylene polymers, when characterized by aratio of corrected optical densities as previously set forth, possess abranched-chain structure which has marked resistance to degradation orfragmentation in the presence of highly active alkylation orcondensation catalysts, such as anhydrous hydrofluoric acid. Thepreferred propylene polymerization conditions utilize a phosphoric acidpolymerization catalyst and yield a polymer mixture having a molecularweight predominantly in the C to Cm range, which mixture upon properfractionation gives a high yield of mono-olefins of the desiredbranched-chain structure boiling within the range of 360 to 520 F.

It should be noted at this point that it is virtually impossible todefine in terms of precise chemical structure the new mixture ofcompounds obtained according to this invention. However,

. the foregoing ratio of optical densities is definitive of chemicaltype structures of components of the mixture and is indicative of therelative proportions, of different types of components containedtherein, as will be apparent from the following discussion.

Infrared absorption bands are caused by natural vibrations of themolecules of a chemical compound. Each atom in a molecule is free tovibrate about the other atoms to which it is bonded and does it with anatural and characteristic frequency. As the molecule is irradiated withlight of this frequency, energy is absorbed by the molecule causing itto vibrate and thereby diminishing the intensity of the light which istransmitted.

Likewise, each pair or characteristic group of atoms in a molecule hasits own natural modes or frequenc of vibration. The difference betweenthe absorption frequencies of different chemical groups are often greatenough to permit positive identification of the principal functionalgroups in a molecule. Thus, by irradiating a chemical compound or amixture of compounds with infrared light to obtain the complete infraredabsorption spectrum of the composition, one may obtain the sum of thecontributions from all of the characteristic chemical or functionalgroups in the material and thereby determine its principal typecomponents or features of chemical structure. Many of the correlationswhich have been made between molecular structures and frequencies ofabsorption bands are given in Table I.

I Thompson and Tor kington, Trans. Faraday Soc. 41,. 246 (1945).

Table II C" Pro- CuMixed Cu Bu- 0., Bupylene Butane tene-l tens-2Polymer Polymer Polymer Polymer D. 10.35 mu l. 308 0. 783 0. 936 0. 835D.@ 11.25 mu 1.020 1.49 1.173 1.04 3, -R factor 1. 2s 0. 525 0. 797 0.803 Ema 10.35 mu=Mol.

Extinction CoeiIicient i3. 08 7. 83 9. 36 8. 35

These data show that the ratio of corrected optical density (Dc) at10.35 mu to correct optical density to 11.25 mu is greater than 1 forolefin chains of polypropylene structure, whereas nonequivalent olefins,exemplified by polymers of the butenes are characterized by a value ofless than 1 for the same ratio. This ratio of corrected opticaldensities at 10.35 mu and 11.25 mu is hereinafter termed R factor.

Likewise, the foregoing data illustrate the fact that the desiredolefins of polypropylene structure possess a molecular (Emol) extinctioncoeflicient greater than 10 and preferably greater than about 12 at10.35 mu, whereas non-equivalent olefins have a molecular extinctioncoeiiicient less than 10 in this band.

The following test procedures are utilized for determining the abovevalues.

Tssr PROCEDURE FOR DETERMINING R Fac'ron Using an infrared spectrometerequipped with liquid cells of approximately 0.1 mm. in thickness,accurate optical density measurements of the olefin sample are madeevery .02 to .04 mu in the 10.35 mu absorption band (for example from10.2 mu to 10.5 mil) and in the 11.25 mu absorption band (for examplefrom 11.1 mu to 11.4 mu).

An infrared spectrum is drawn plotting optical density as the ordinantv. wave length as the abscissae. The molecular weight and specificgravity of the olefin sample are measured by the usual methods. Theoptical density values corresponding to the peak of the absorbed bandnear 10.35 mu and near 11.25 mu are read from the spectrum, and each iscorrected to a molecular weight basis of and a specific gravity of 1 asfollows:

D D (measured)X (mol. wt.) X1

(Specific gravity) X 100 R factor is then determined as follows:

D at 10.35 mu D, at 11.25 mu A value greater than unity for the R factorindicates a satisfactory propylene polymer and a r v d polymer having arelatively high proportion of color bodies frequentl present inullsulfonatable E 10.35 mu= (ape oleflns with the structure: residue areremovable only with considerable dit- R C C RI flculty, it at all.

I Significant diiferences in chemical structure 5 and composition or themixed phenyl-sulionate All R. factor less han unity indicates 8 P 3substituted alkanes of this invention are shown which iS subject todegradation and iragmentaby the following data on detergency; tion inthe presence of-active alkylation or condensation catalysts and showsthat the polymer Table 7 mixture contains a relatively high proportionof m ,Detergency oleflns mm the structure: Polybutene phenyl-sulfonate(12 aliphatic H carbons) 1 Polypropylene phenyl-sulfouate (co alkyl) 46i I r Measured by relative whiteness of cleansed fabric. TEST PRMmmE-Smum-ll As previously indicated the exact chemical con- EXTINCTIONCOEFFICIENT stitution oi. the compositions produced according Theoptical density of the olefin sample corto ,this invention cannot beprecisely defined. responding to the peak of the absorption bandHowever. the infrared absorption spectrum clearnear 10.35 mu is obtainedas in the test proly indicates that the olefins of polypropylene cedurefor determining R factor. From this structure are largely of the type:measured optical density the measured molecular weight of the sample andthe measured specific gravity, the molecular extinction coeillcient iscalculated as follows:

D(measured at 10.35 mu) X(mol. wt.) cific gravity) X (thickness ofsample in centimeters) Values greater than 10 for Enrol at 10.35 mu andrather than preferably greater than 12 indicate a satisfactory 3opolymerhaving a relatively high concentration of oleflns of thestructure: H

H It appears necessarily to follow that the phenyl Non-equivalency ofdifierent branched-chain polypropylene alkanes and the sulfonatesthereof oleflns in the HF alkylation of benzene are illusare complexmixtures characterized by the trated by the following: branched-chainstructure of polypropylene and Table III R factor E 1 10.35 mu mo and HFW M Yield Cu Cut Sm tion (In Polypropylene greater than 1... greaterthan 10-. 8Q% less thm 127. O Polybutenes oss t a 1 1888 than 10--..less than 30%-.-- approx. 0

Distinctions and non-equivalency of the rea tertiary alkyl carbon atomat the benzene ring sulting mixtures of phenyl alkanes after fraction-50 thus:

ation of the crude alkylate to separate a C1: al-

kane derivative is illustrated by the data in Table IV: r V H l H TableIV Br-RI Phenyl Sulionate Unsulio- Color 012 alkane; Per notable centYield Residue Polypropylene, 01a Alkylgood- 100% approx none. 50 ate. rPolybutene, C1rAlky1ate. poor.-. 25%. H H

. i 1-Rr In the foregoing tables references to "Cu out" and C13 alkylatedesignate the Cu alkane fractions which, by addition of the six carbonatoms on: of the phenyl group, become C1: fractions or alkylate.

Even relatively small percentages of unsultonated residue may impart anundesirable odor V to the sulfonated product particularly on aging wherex is hydrogen or a hydrogen equivalent and such small odor-producingresidue have not of a metal. Since these compounds are charbeensuccessfully eliminated by any known. proacterizcdby the branched chainstructure of polycedure in various instances. These objectionablepropylene R1 and R: are of the type formula odors are especially to beavoided in the produc-- Conan as are all acyclic alkane radicals and attion of detergents. Additionally, last traces oi least one It is of p yppylene structure.

On the contrary it necessarily appears that oleflns of the structurewhich characterize the polybutene mixtures must yield either degradationproducts of unknown constitution or by known laws of substitution willgive phenyl alkanes in which the alkyl carbon atom at the benzene ringis quaternary rather than tertiary:

H R- JH The new mixture of phenyl alkanes preferably,

less desirable.

The crude alkylate is fractionated to yield novel phenyl alkanecompositions and preferably the desired fraction is sulfonated to yieldan improved detergent as hereinafter disclosed.

Olefins oi the preferred structure may be obtained by polymerization ofsubstantially pure propylene under suitable conditions to form a complexmixture of alkenes' having an average molecular weight corresponding topolymers containing from about 12 to about 15 alkyl carbon atoms.Additionally there is formed other higher and lower molecular weightpolymers from which the C12 to C15 fraction desirably is separated.Mixtures of propylene with saturated low molecular weight hydrocarbonswhich do not enter the polymerization reaction may be used as a feedstock; for example, propylene containing propane, ethane and methane.Further, a mixture of such hydrocarbons containing ethylene is notprecluded since the ethylene enters the reaction only to a minor extent.However, the propylene feed preferably should be substantially free ofimpurities such as isobutenes which tend to produce instability in thechain structure or to lower the R factor below unity and the molecularextinction coeflicient beiow 10. Likewise, the amount of normal buteneimpurities should be kept at a minimum, for example, less than 1% Onemethod of polymerizing the propylene feed to obtain the preferred typeof alkene comprises contacting the hydrocarbon mixture with a phosphorioacid catalyst, for example with a catalyst formed by saturating asupport such as a kieselguhr or activated charcoal with 75%orthophosphoric acid. Catalyst temperature may vary from 300 F. to 500F. and feed rate from 0.25 to 1.15 volumes of gas, per volume ofcatalyst per hour. Pressure may be atmospheric although higher pressuresare preferred, for example, 200 to 600 pounds per square inch. Thresulting polymer product is a mixture of oleiins from which therelatively stable acyclic branchedchain polypropylenes utilized in thepresent inzention are obtained by close fractional distillaion.

Preferably the polypropylenes to be converted to the final alkanes inaccordance with this invention should boil within the range of fromabout 300 F. to 600 F., more desirably within the range of from about325 F. to 520 F., and

by volume to maintain the R factor or molecular extinction coefficientat the optimum value.

A suitable feed stock for polymerization is pure propylene or a mixturesuch as the following:

preferably within the range of from 360 to 520 F. At least about 50% ofsuch polypropylene fractions preferably should boil above 380 F. It hasbeen discovered that a mixture of polypropylenes having an initialboiling point of from 360 F. to about 370 F. and an end point of from465 F. to about 520 F. with at least 50% boiling above about 390 F.,upon conversion to the corresponding phenyl-sulfonate substituted.alkanes yields a superior detergent. Again, the polymer mixture may befractionated to yield a C12 polypropylene out having a boiling rangefrom about 330 F. to about-420 F., at least about 50% of which boilsabove 350 F. and a C15 polypropylene fraction having a boiling range offrom about 420 F. to about 510 F., at least about 50% of which boilsabove 450 F. Each of these fractions may likewise be converted to phenylalkanes and to the sulfonate derivative thereof. The foregoing boilingranges are determined by an AS'IM-D-SG standard distillation.

Unsaturation of the polymer fractions desirably should correspondsubstantially to that of the mono-olefins. Inspections of exemplary C12and C15 polypropylene fractions are as follows:

EXAMPLE 1 Tetramer Test Data Gravity (A. R. 1.). Index of Refraction n Yscosity at F Viscosity at 210 F.

1.43'10. 1.228 Centistckes.

Bromine Number Cennsmkes' ExAnPLE 2 Pentamer Test Data Boiling Range(760 mm.) 420-510" F. Gravity (A. P. I.) 45.3. Index of Refraction111).. 1.4502. 7 Viscos ty at 100 F 2.33 Centistokes. Viscosity at 210 F0.974 Ccntlstokes.

Distillation of the pentamer in a Stedman still gave the followingresults:

Parts by Equivalent Volume 121. 13 Pressure Vapor (liquid) O (mm.Hg)Temp., F. Overhead at 760 mm.

The following additional distillations exemplify typical molecularweight distributions of selected polypropylene fractions possessing an Rfactor greated than 1 and a molecular extinction coefficient greaterthan 10.

1 These are vapor-line temperatures.

Olefins of the foregoing structures and molecular weight distributionare condensed with an aromatic hydrocarbon of the benzene series in thepresence of a hydrofluoric acid catalyst, as previously stated, to formthe mixture of phenyl alkanes of this invention. Condensation of theolefine with benzene is preferred but toluene or xylene also is embracedwithin the broader aspects of the invention. Likewise, the inventionalso includes in its broader aspects condensation of the olefins withbenzene sulfonic acid, that is to say, sulfonation of the benzenenucleus can be effected before rather than after the alkylation orcondensation stage of the process, although such procedure is presentlyregarded as less desirable.

A hydrofluoric acid catalyst has been found highly advantageous forefiecting the foregoing condensation reactions of polypropylenes withbenzene, despite the fact that prior literature and experience indicatesthat this catalyst acts severely to decompose branched-chain oleflnsinto shorter chain fragments during the condensation reaction. When theolefin is of the structure and composition herein disclosed, thecondensation reaction goes smoothly with minimum formation ofundesirable side reaction products characteristic of chain fragmentationor degradation.

As indicated in Fig. 1 of the drawing benzene, hydrofluoric acidcatalyst and the selected polypropylene fraction are passed to analkylation reaction chamber. Relatively large amounts of hydrofluoricacid such as 200 to 800 mol per cent based on the olefin are suitable.Since the olefin is relatively expensive, an excessof thebenzen'e isusually adopted to effect more complete con-. version of thepolypropylene to phenyl alkane and to minimize a condensation of two ormore olefin molecules with the same aromatic nucleus. Upon completion ofthe reaction the hydrofluoric acid catalyst is separated from thealkylationmixture, as by vaporization, and residual traces thereof maybe removed by washing with aqueous alkali.

Following the line of flow in Fig. 1, the alkylation mixture isdistilled first to remove excess benzene (which is recycled to thealkylation stage) and then to separateas overhead the monophenyl alkanesboiling within the range of 370 to 650 F. The preferred phenyl alkanesof this invention boil within the range of from about 475 F. to about650 F. and more desirably within the range of from about 500 F. to about625 F. Despite the fact that an excess of benzene is utilized during thealkylation reaction, some readily separable heavy dialkyl benzenes areformed containing two C1: polypropylenechains on a single benzenenucleus. These heavy dialkylbenzenes are separated as distillationbottoms and may be withdrawn from the system or in some instancesrecycled to the alkylation stage as indicated by the dotted flow line ofFig. 1.

In those cases where the original olefin is a polypropylene having an Rfactor greater than 1 and a molecular extinction coeflicient greaterthan 12, it has been found that the phenyl alkane overhead fractionsboiling within the ranges above indicated are of superior purity. Thesealkanes are substantially free of objectionable color bodies, yieldlittle or no unsulfonatable residue, and contain substantially the samenumber of carbon atoms in the single alkane chain of the molecule aswere present in the original alkene. The relatively high purity andstability of the phenyl alkane products of the reaction makes possiblethe production of sulfonates and other derivatives without the necessityfor decolorizing treatments with adsorbents or stabilization by sulfuricacid treatment which heretofore has complicated the production of suchderivatlves. Also, it has been found that the high purity and stabilityof the phenyl alkanes of this invention yields sulfonates which arerelatively free of undesirable odor not only immediately after theirproduction but after long periods of storage during which. time variousother sulfonates derived from petroleum raw materials have developedobjectionable odors.

In practicing the invention according to Fig. 1 of the drawing, thephenyl alkane fraction is next sulfonated with. any suitable sulfonatingagent, such as chloro-sulfonic acid or, preferably, a fuming sulfuricacid. A suitable sulfonating agent is from 5 to 25% fuming H2804 in theratio of from 2 to 5 mols of acid per mol phenyl alkane. About 3 mols ofacid per mol of alkane is preferred. The temperature during initialstages of the sulfonation reaction desirably should be kept below F. bycooling and adding the acid slowly to the phenyl alkane. To obtainsubstantially complete reaction temperatures above about 90 F. should bereachedup.to about F. is permissible. Thorough agitation should bemaintained, and local overheating avoided to either with or withoutaddition of water, and the acid discarded. A desired amount of the acidlayer may be neutralized and returned to the sulfonated hydrocarbonmixture as indicated by dotted lines to control sodium sulfate contentthereof. 7

The sulfonated hydrocarbons are next sent to a neutralization stagewhere caustic alkali solution is added to form the sodium salt of thesul-' fonic acid radical now attached to the phenyl group of the alkaneby reason of the sulfonation treatment. The neutralized phenyl-sulfonatesubstituted alkane flows in the form-of an aqueous slurry or paste to asuitable drier where the finished detergent. product is obtained.

The sulfonate product is a complex mixture of substituted alkanes inwhich the alkane portion of the molecule corresponds substantially inmolecular weight and structure to that of the original olefin. Thephenyl sulfonate substituent on the alkane chain furnishes a polargroup,

which is correctly balanced with the non-polar hydrocarbon structure toyield an excellent detergent. This sulfonate detergent may be used insubstantially pure form but is preferably oompounded with builders,additives,auxiliary detergents or the like.

One particularly desirable form of detergent is produced by drum-dryingor spray-drying slurry containing sodium sulfate and the neutralizedphenyl sulfonated substituted alkanes in proportions to yield a driedproduct containing from about 50 to about 70% by weight, preferably 55to 65% by weight of sodium sulfate. Other inorganic builders such astetrasodium pyrophosphate, sodium silicate, trisodium phosphate and thelike may be incorporated in detergent compositions containing the mixedsulfonates herein disclosed; A typical composition is as follows:

Exmts 4 Percent by weight 1 Bulfonate Sulfate Tetra-sodium pyrophosphateSodium silicate 1 Additionally, organic additives may be incorporated incompositions such as the foregoing to enhance the detergency action ofthe sulfonate on diflicult fabrics or stubborn soils. One such suitableadditive is a carboxymethyl cellulose sodium salt. This composition maybe derived from cellulose by reaction of alkali cellulose withchloracetic acid to form a carboxylicether which is converted to thesodium salt. A suitable composition is available in commercial formunder the name "Carboxymethyl Cellulose Sodium Salt (medium viscositygrade). From 1 to 20% of this additive may be incorporated in adetergent mixture containing about 60% sodium sulfate and 40% sulfonatedetergent. It has been Reference to Figs. 2, 3 and 4 of the drawing willreveal a detailed flow sheet illustrating an embodiment of theinvention, wherein production of a suitable olefin from propylene iseffected in Fig. 2, the olefin and benzene are converted to the desiredphenyl alkane in Fig. 3, and the alkane is sulfonated and neutralized toyield the desired detergent in Fig. 4. These three figures when placedside by side from left to right in numerical order form a complete flowsheet of a preferred process.

Beginning with Fig.2 there is provided a polymerization chamber HI fromwhich the reaction mixture is passed first to a stripper H for removingthe more volatile components such as fixed gases and then to afractionator l2 forseparating C11 and lower oleiins as overhead. Asecond fractionator l3 receives the bottoms from fractionator l2 andseparates a C1: olefin mixture as an overhead fraction. Finalfractionator l4 separates the bottoms from fractionator l3 into a C15olefln mixture as overhead and heavier than C15 hydrocarbons as bottoms.When desired fractionators l3 and I4 may be combined into onefractionation stage with separation of a single mixed Cu to C15 oleflncut.

A mixture of C1: to C15 olefins obtained either by blending the separateC12 and C15 fractions or from the single stage C1: to C15 fractionatoris fed to the alkylation stage of Fig 3 by way of line l8 and an excessof benzene by valve-controlled inlet line H. The two hydrocarboncomponents are mixed in line l8 after which they are dehydrated infractionating column IS., The dehydrated hydrocarbon mixture then flowsby way of line 2| to a sealed contactor 22 provided with a garoling coil23 for controlling reaction tempera- Hydrofluoric acid catalyst isintroduced into contactor 22 by way of feed line 24 and is intimatelycontacted with the hydrocarbon reactants by the vigorous action ofagitator 26. The hydrofluoric acid catalyzes the condensation of thepolypropylene with the benzene feed to form monophenyl alkanes of thetype previously described. Temperature is controlled and exothermic heatof reaction removed by circulatin any suitable refrigerant throughcooling coil 23.

I As the reaction mixture flows upwardly hrough contactor 22, it passesby way of dis-" fonated is recovered as overhead. This phenyl alkaneoverhead flows from distillation column 33 by way of line 34 to thesulfonation system of Fig. 4.

The phenyl alkane flowing by way of conduit 34, when desired, may besubjected to a preliminary color extraction stabilizing treatment in acontactor at 38 or this contactor may be bypassed and the phenyl alkanesent directly to sulfonator 31. The sulfonated reaction mixture passesby way of overflow line 33 to settler 39 when it is desired to removeexcess acid, and the sulfonic acid phase then flows to neutralizer 4|.Upon addition of caustic soda to the sulfonic acids in neutralizer 4|,the sodium sulfonates thereby arr-aces formed pass to a spray dryer 4!with or without. further treatment subsequently to be described. Thedried detergent preferably is promptly pack: aged as a finished articleof commerce. 1 l i The foregoing is a general description of the processrepresented by Figs. 2, 3 and 4 of the drawing. In order tofacilitatepractice of the invention and design of .asuitable commercial plant, thefollowing more specificdescription is submitted.

Referring. to Fig. 2, propylene onlymay be fed or, as here shown; Cs-Cuoleflns selectedfrom the group consisting of straight-chain oleflns andpolypropylene are fed by way of inlet line 5| together with propylene byway of inlet line 5| to mixer 52. The resulting olefin mixture thenpasses through preheater 53 and feed line 54 to a.

fixed bed solid phosphoric acid catalyst in polymerization chamber It.Steam also is introduced into the polymerization chamber by way of line56 in a quantity suillcient to maintain a partial pressure of watervapor equal to that of the phosphoric acid catalyst in order :to preventdehydration of the catalyst whichis maintained at i the. desiredreaction temperature by heat of reaction. Inter-polymerization of thepropylene with the C4! to C11 olefins, preferably polypropylene, iseifected upon. contact with the polymerization-catalyst, as they flowdownwardly through 1 the catalyst bed, and the resulting polymerizedmixture is then conducted by way of conduit 51 through heat exchanger 53to stripper column II where low boiling hydrocarbons are removed asoverhead through line 58. The gases removed in stripper H comprisemostly propane and propene together with other hydrocarbons containinless than five carbon atoms. The stripped gas flows through cooler 59 tocollecting drum 8| wherehuncondensed gases may be discharged by way ofvent line 62. 1

In order to regulate the temperature developed by exothermic heat ofreaction in the polymerization zone, a controlled portion of the cooledgases and any condensate formed in. drum BI is conveyed by way of valvecontrolled line 3 and introduced into the polymerization zone as adiluent and cooling gas. To further facilitate con-- trol of reactiontemperature, valve-controlled conduit 64 is provided for by-passing someof the reaction feed directly to the polymerization zone withoutpreheating by heat heater 53. i

The polymerized mixture, stripped OfCs and lighter gases, flows from thebottom of column II by way of conduit it to the firstfractiorafor I!where light olefin polymers in the Co to Cu range are separated as avapor phase overhead. which passes by way of outlet conduit 61 throughcondenser 68 to condensate drum i9. Fractiona- .exchange in pretion iscontrolled and improved by returning a portion of the condensate fromdrum 6! to frac: tionator I! by way of valve-controlled reflux line I I.

To increase the yield of C1: to C1: olefins, it is sometimes desirableto return at least a portion of the C6 to Cu olefins (separated infractionator I!) by way of valve-controlled line I2 to polymerizationzone Ill and thereby cause inter-poly .merization of these lowerpolymers with the propylene feed to yield additional C1: to C15 olefins.Excess Co to Cu olefins may be withdrawn by means of discharge line II.

TheCn and higher boiling olefin polymers pass downwardly throughfractionating column I! and out discharge line ll through pressureretion of the C12 olefin cut by way ofvalve-con trolled line 82 throughpump 83 to inlet feed mixer 52. The remainder of the C12 olefin cut ispumped through conduit 84 to tankage for blending with the C15 olefincut obtained in the next fractionation stage.

The C15 and higher boiling olefins flow downwardly through fractionatingcolumn [3 and are discharged by way of line 86 through pressure reducingvalve 81 into fract onator H where a C15 olefin fraction boiling, forexample, from about 420 F. to about 500 F. at atmospheric pressure istaken overhead through condenser 88 to condensate drum 89. A portion ofthe condensate may be returned to iractionator l4 byway ofvalve-controlled reflux line 9| and the remainder pumped to tankagethrough line 92 for blending with the C12 fraction. Bottoms fromfractionator H are discharged to outlet line 93.

It is preferred to operate fractionating column II as well as column l3under vacuum in order to avoid deterioration of the C1: to C15 olefinsby decomposition or further polymerization. De-

sirably, fractionator I4 is maintained at higher vacuum thanfractionator 13 by means of a vacuum line ill on condensate drum 88 andconnected to any suitable device for maintaining reduced pressure, suchas vacuum pump, or steam ejector.

To illustrate suitable operations in the foregoing process, exemplarypolymerization conditions are:

Exsurur 5 Temperature of fresh feed 350-425 1''. Temperature of cat- 1alyst 375-500 F. (preferably 400-460 F.) i Pressure 200-600 lbs/sq. inPropylene feed (as liquid) .02-0.2 v./v./hr. Catalyst IOU-%orthophosphoric acid on kieselguhr A typical feed stock will containother normally gaseous hydrocarbons in various proportions, such as thefollowing:

\ 3 Exmru: 6'

Hydrocarbon: Volume per cent Ethylene 3.2 Ethane 2.6 Propylene 16.0Propane 57.5 Butene (impurity) g 0.1 Butane 3.7

The remaining 16.9% of the feed stock may be C to C11 propylene polymerspreviously formed gar-mas by polymerization under substantially the sameconditions or it may be a'mixture of Co to Cu normal oleflns aspreviously indicated.

The effect of the amount of Ct to Cu propylene polymers on the yield ofCr-a-Cwinterpolymers obtainedwith propylene is illustrated by thefollowingdata: I

Relative Relative Percent n Volume Volume to Cu Pro ylene Coto 0n Olefinin in eed in Food Polymer At least about 0.2 liquid volumes of Ce toCnpolypropylene per liquid volume of propylene is desirable. Morethan tenvolumes per volume of propylene usually is not warranted. In theforegoing runs the average temperature of catalyst was 430 F., pressure,200 pounds per square inch gauge; and propylene feed rate, .032v./v./hr. Higher pressures increasethe yield of Cu to Cf s olefininterpolymers as illustrated by the followin data:

In some situations it ls, therefore, preferred to operate the process at400 to 600 pounds per square inch pressure. In these latter runs,average catalyst temperature was 430 Fo and the ratio of Ca to Cuoleiins to propylene was approximately 2.221.

Although the C12 and the C15 olefin fractions may be alkylatedseparately, preferably a blend of from 60 to 80% of the foregoing C12olefin fraction with from 40-20% of the C15 fraction is prepared byconveying these respective oleflns from tankageby way ofvalve-controlled outlet lines 9,6 and 9! to blending tank 93. Theblended olefin boiling within the ranges hereindisclosed, thenfiowstogether with benzene from valve-controlled benzene feed line I! byway of suli'onation inlet conduit I8 to the alkylation stage of Fig. 3.

The benzene olefln mixture from the polymerization system is firstdehydrated in fractionating column I9 of Fig. 3. This dehydrating columnis operated under total reflux." In such an operation, water togetherwith a portion of the hydrocarbons is vaporized overhead, passes throughline IOI to condenser I02, and the condensate collected and allowed tostratify in condensate drum I03. The lower water layer is removed byline: I33 and the hydrocarbon layer returned to fractionating column I 3by way of reflux line I03. The dehydrated hydrocarbon feed passes fromthe hot.-

16 cooler I01 to reactor 22. Condensation of the polypropylene with thebenzene is effected by cataiysis with hydrogen fluoride in reactor 22,and

the temperature is controlled by indirect heat reactants, it isimportant that intimate contact between the hydrocarbon and hydrofluoricacid phasesbe eliected by vigorous agitation. As here shown, an agitator26 is provided and is driven by motor I09 connected thereto by shaft IIIpassing'through the bottom of reactor 22. In the construction of thisagitator it has been found advantageous not only to provide ahydrofluoric acid resistant bearing and packing for shaft ill, but alsoto flush this bearing and packing with fresh benzene admitted by way ofvalve-controlled line 'l I2 whereby minimum exposure to the action ofhydrofluoric acid is obtained.

After the hydrogen fluoride catalyzed condensation has been effected inreactor 22,-the reaction mixture is passed'through overflow conduit 21to settler 28 where a lower hydrofluoric acid phase and an upperhydrocarbon phase are formed. The lower acid phase is withdrawnfrom thebottom'of settler 28 through cin iduit H3 and may be recycled to thereactor by way of valvecontrolled return line III or passed to thehydrofluoric acid purification unit, hereafter described, by way ofvalve-controlled line H6.

The oil phase in the upper portion of settler 23 contains the excessbenzene as well as some hydrofluoric acid together with the condensationreaction products. This oil phase is continuously withdrawn throughoverflow II I and passes through heater lid to benzene stripping column23 where benzene and hydrofluoric acid are vaporized as overhead and areconducted through line I2I and condenser I22 to condensate drum I23. Inorder to improve the separation of benzene a portion of the hydrocarbondistillate collected in condensate drum I23 may be returned to stripper29 by way of reflux line I23. The benzene-hydrofluoric acid mixture iswithdrawn from condensate drum I23 through line I26 and may be processedas hereinafter described in more detail in one of three ways; namely, bypassing the mixture through valve-controlled line I21 to thehydrofluoric acid recovery system, by recycling directly to reactor 22through valve-controlled return line I28, or by feeding thebenzene-hydrofluoric acid mixture through valve-controlled line I23 to asuitable fractionator for separating the two components. I

Returning now to the benzene stripper 2!, the hydrocarbon reactionmixture stripped of its benzene and most of the hydrofluoric acidcontained therein flows from the bottom of said stripper through outletline I3I to a lime or'bauxite packed treater I32. In order to facilitatecontinuous operation, two or more of these treating chambers may beconnected in parallel so that,

mixture flows from the bottomof treater I32 through line I33 to causticwasher 3Iwhere final traces of organic fluorides are decomposed or tomof column I3 through outlet conduit 2| extracted.

Washer 3| contains a lower aqueous caustic ayer I34 and an upper waterlayer I36. The in-fl ;erface between these two layers is indicated bylotted line I31. Desirably aqueous caustic is in- ;roduced by pump I38at washer inlet pipe I39 n the upper zone of the aqueous alkali layerand :irculated downwardly to pump return line I4I. Fresh caustic may beintroduced and spent caus- ;ic discharged by suitable connections notshown. Water is likewise preferably circulated from upper inlet I42 tolower outlet I43 in order to provide a countercurrent washing action forremoving any entrained caustic. Thus, the hy- :lrocarbon feed introducedby line I33 flows upwardly through first an aqueous caustic, thenthrough a water layer in washer 3I to outlet conduit I44 andfractionator 32.

Lower-boiling hydrocarbons are separated and the reaction mixturereduced to the desired initial boiling point by vaporization infractionator 32. The vapor-phase hydrocarbons are taken as overheadthrough line I46 and condenser I41 to condensate drum I48. Improvedfractionation is obtained by returning a portion of the condensatethrough reflux line I49 to fractionator 32. Condensed hydrocarbons areremoved from the condensate drum by way of line I 5| and may, whendesired, be recycled to reactor 22. The remaining hydrocarbonsconsisting essentially of mono-phenyl alkanes and having an initialboiling point within the range for example of from 350to 370 F. arepassed from the bottom of fractionator 32 through line I52 tofractionator 33.

.Monophenyl alkane product is distilled over head from fractionator 33through line I53 and i condenser I54 to condensate drum I56. Producthaving, an initial boiling point as above described and an end point forexample of from 600 to 610 F. is withdrawn by way of line 34 and passedto the sulfonation stage described in connection with Fig. 4. Beforeproceeding with a description of the sulfonation of this monophenyl a1-kane product, the hydrofluoric acid recovery system of Fig. 3 willbedescribed.

In the continuous operation of the hydrofluoric acid catalyzedalkylationor condensation system,

the hydrofluoric acid catalyst becomes contaminated with water and andacid oil until its eflicacy as a catalyst is substantially diminisheddespite thefac t that the hydrocarbon feed is carefully dehydratedas-described. Thus, the hydrofluoric acid layer separated in settler 23becomes an aqueousmixture whichtmust be either discarded or be suitablytreated to recover and purify the same. In a preferred operation, thisacid layer one portion thereof is either intermittently or continuouslyconducted to a purification unit by wayof valve-controlled line I'I6.

Purification and recovery of the contaminated hydrofluoric acid presentsa problem by reason; of constant boiling mixtures which the acid formswith its contaminants. In order to facilitate recoveryand purification,fresh benzene is introduced by way of valve-controlled line I 51into theaqueous mixture of line H6 and passed through Preheater I53 tofractionating column I59. In this column benzene acts as a strippingagent and carries hydrogen fluoride as vapor phase overhead throughcondenser I6I to condensate drum I62. A portion of the condensate isreturnedas reflux through line I63 to fractionating column I59. Theremaining hydrogen fluoride-benzene condensate is recycled via line I64to reactor 22. Bottoms from fractionator I59 comprise a constant boilingmixture of hydros fluoric acid and water together with acid oilcontaminants and are withdrawn through discharge line I66. Fractionatingcolumn I59 thus effects a split between benzene and hydrofluoric acid onthe one hand and a constant boiling aqueous hydrofluoricacid mixture onthe-other hand.

Instead of, or in addition to, the fresh benzene fed to fractionator I59by way of line I51, the benzene hydrofluoric acid mixture from benzenestripper condensate drum I23 may be introduced by way ofvalve-controlled line I21 into HF recovery line II6 as previouslyindicated. The relatively large excess of benzene in the mixture fromcondensate drum I23 serves as a strippin agent and permits economy Inthe use of fresh benzene.

Alternatively, a portion or all of the benzenevapor phase hydrofluoricacid passes overhead through line I68 and condenser I69 to condensatedrum IN. The fractionator may be operated under reflux by returning aportion of the condensate through reflux line I12. Hydrofluoric acidfrom condensate drum "I is recycled to reactor 22 by way of line I13 andreturn line I14 to catalyst inlet I08. Benzene from, the bottom offractionator I61 is recycled to reactor 22 through return line I16.

Exemplary operating data for the manufacture of monophenyl alkanes inaccordance withthe foregoing process stage and utilizing anhydroushydrofluoric acid as a catalyst are:

Aromatic feed Benzene Propylene polymer feed:

Initial boiling point (ASTM). ."F 362. End point (ASTM) ....F.. 464Gravity (A. P. I.) 47.1

Bromine number 103.1

' 1 Feed mixture 10: 1 benzene to polymer mol ratio.

Reaction conditions Crude reaction product Bromine number: 0.9' PercentF: nil to 0.1

"crud n'enyl alkanes (ASTM distillation) vomme "per centlighter than 520F 7.5

Volume percent boiling 520 F. to 600 F 860 Volume per-cent bottoms(boiling above about 600 F.)..- 6.5

Yields In order to guide those skilled in the art'in the chemistry ofthe process and of the compositions of this invention, and to moreadequately illustrate the preparation of monophenyl alkanes from C12 andfrom C15 polypropylene fractions, the following simplified specificexamples are given:

Eximrrr:

One hundred milliliters of benzene (87 grams) and 270 grams of anhydroushydrofluoric acid were placed in a stainless steel, closed reactionflask equipped with a metal stirrer and immersed in an ice bath. A feedstock consisting of 227 grams of an acyclic propylene tetramer and 527grams of benzene was added over a period of minutes while stirringcontinuously. The reaction mixture was stirred for an additional fourhours at ice bath temperature and then neutralized with an aqueouspotassiumhydroxide solution to remove the hydrofluoric acid catalyst.The aqueous layer was separated from the crude reaction product anddiscarded. After drying over sodiumbicarbonate and filtering, 790.5

grams of crude reaction product was obtained 20 tion of this tetramerrevealed the following distribution of isomeric dodecenes according tothe boiling range:

Temperature F.

Percent (corrected to EXAMPLE 11 825 grams of benzene and 266 grams ofanhydrous hydrofluoric acid were placed in a stainless steel flaskequipped with a metal stirrer and cooled by an ice water bath as inExample 10. A feed stock consisting of 861 grams of propylene tetramerfraction and 1106 grams of benzene was added over a period of 66minutes, and the reaction allowed to proceed for an additional 60minutes with stirring at ice bath temperature. The reaction mixture wasdiluted with ice and neutralized with aqueous potassium hydroxidesolution, after which the aqueous layer was drawn off and discarded. Thecrude reaction mixture was next washed with distilled water, dried byshaking with sodium bicarbonate and filtered to obtain 2700 grams (97%)of product dissolved in excess benzene. Distillation of this mixture toobtain the monophenyl alkane gave the fcllowing yields:

(yield=94%). This crude reaction product was Volume Weight Boilin Randistilled to obtain the monophenyl alkane frac Fmmn Percent gm oF'atgmog tion as follows. a

' 4 la nzen rra cga l 175-455 Distillation Range! Volume 0110p y ecanes-45cm (927 from 510-550 Fraction at hfgg Percent Bottoms 3.9 143 0 25.;

Benzene fraction; 11545021 o1 The monophenyl dodecane fraction was 80.5%f83f3ifffffif:::::: Z3 FIIIIII of the total alkylaie after removal ofexcess hen; zene; 11.5% of the alkylate'was lost to overhead Gravity (A.P. I.)

Refractive index n5 1.4884 Specific dispersion..-' 128 Viscosity at 100F centistokes 6.60 Viscosity at 210 F do 1.80

This product was essentially a mixture of isomeric monophenyl dodecanesof polypropylene structure believed to contain approximately five methylgroups in the alkane portion of the molecule.

The propylene tetramer fraction utilized in the preparation of theforegoing compound had an A. P. I. gravity of 51.5, a bromine number of85, and a boiling range of 325 F. to 400 F. Distillabenzene cut andabout 8.0% was lost to distillation bottoms. Conversion of olefin toalkylate was essentially Inspections on the monophenyl dodecane frac-ftion were:

Gravity (A. P. 1.)--- 31.4 Specific dispersion 131 Refractive index .n1.4874

The propylene te-tramer fraction utilized in the preparationof theforegoing compound was characterized by the following inspections:

Boiling range at 760 mm F 340-420 Gravity (A.P. I.) 51.6 Refractiveindex n 1.4370 Viscosity at 100 F centistokes 1.228 Viscosity at 210 Fdo .644 Bromine Number L 92.

EXAMPLE 12 The monophenyl pentadecane fraction was pre-' pared bycondensing the propylene pentamerof Example 2 with benzene in thepresence of anhydrous hydrofluoric acid as a catalyst by a Probe I duresubstantially as described in Examples 10 21 o o and 11 above. The dataon two such preparations may be summarized as followst Continuing nowwith the flow sheet and conversion of the monophenyl alkanes-flrst to aphenyl The foregoing mixtures of monophenyl alkanes are believed to benovel compositions of matter and possess a unique combination ofproperties.

These new and unpredictablecharacteristics are illustrated bycomparisonwith alkyl benzenes derived by. alkylation of benzene withmixed butene polymers in the C12 to C16 range. In comparative testsalkylationof benzene with C12 olefins from mixed .butenes (boiling range350 F. to 400 F.', A.\P,. I. gravity 45.2) yielded only 29% of alkylatehaving a molecular weight correspondin to that of the alkenes.Approximately 48% of the olefin 1 was lost tolight alkylate by reason ofdegradation or fragmentation, and about 23% was lostto distillationbottoms. Conversion of olefin to alkylate was about 86.3%. In contrastthereto, alkylation of benzene with a C12 polypropylene boilingforremoval, nd only 74.4% of the alkyl benzene was convertible tothesulfonate. On the other hand, 97.2%,of the monophenyldodecaneifraction from polypropylene was converted to the desiredsulfonate and required no purification. Sig,- nifioant distinctions inthe structure otthe mixed butene alkylate and the monophenyl dodecanesfrom polypropylene are shown by the fact that in a detergency test at0.2% concentration (60% sodium sulfatewith 40% sodium sulfonate) undercomparable conditions, the polybutene bena zene sulfonate gave a valueof l as compared with auvalue 01746 for the sulfonated monopheriyldodecane fraction from I polypropylene.

Run A Run B Pentodecme Impectiom Boiling Range (760 mm.) 420 510 F42c-s2o r. 1 Gravity, A. P. T 45.3 44.7. i Bromine Number o o 102.

Reaction Conditions Mo]. Ratio (pentadecene:benzene:HF)...L l:5.3:2.5116:4. Tnmpemhim 100 Bath 108 Bath. Pressur Atmospher Atmospheric.Vessel Stainless steel Stainless steel. Addition time 51 minutes.-. 60minutes. Reaction m minutes 3.75 hours.

Yield Data Reactants used: o

Pemadecenn 627 Rm 738 gm. Benzeneii 1246 gm 1640 gm. Crude yield afterwash 1777 Pm 2270 gm. Crude yield, percent.. 9 95.5.

Distillation Chm-m: 1742 Fm 2270 gm.

Vol.,percent Wt., gm. Vol.,percent Wt, gm.

Cuts:

N o. l (benzene) 1302 69 1567 No.3 (monopbenyl pentadecanes). 320 w 25568 No. 4 (bottoms) 120 6 135 Boiling Ranges at 760 mm. 1 No. 3(monophenyl pentadecanes) 515-664" F. (63% from 520-680 F. (82% from680-63 580-630). Percent Theoretical Yield 37 2 65.6. Percent ofPentadecene to Bottoms 16.1 14.3.

Inspections on Monophem Z pmtudecams Gravity, A. P. T i 9 30.6.Specifier pm inn I29 128, Refractive Index no" 1.4850 1.4886.

sulfonio acid-substituted alkane, and then to the sodium salt thereof,reference to Fig. 4 will reveal that the complex mixture of monophenylalkanes from fractionator 33 flows through line to the sulfonate processstage.

Ordinarily the phenyl alkanes of this invention may be sulfonateddirectly without further treatment, but provision is made in Fig. 4 forcolor stabilization and correction of off-color products by apreliminary extraction with a selective solvent for color bodies andtheir precursors. As here shown, the phenyl alkane may be sent totreator 36 through valve-controlled line I80 and contacted with aselective solvent for color bodies, preferablysulfuric acid. Thispreliminary treatment desirably is of controlled severity (wellunderstood in the art) sufiicient to reach and selectively extractcolorbodies and unstable compounds, likely to form color bodies, but insufficient to sulfonate the phenyl alkanes in signifi- V cant amounts.Suitable acid concentrations and treating temperatures arefrom 95 to 98%sulfuric acid at to F. The phenyl alkanes are thoroughly contacted withthe acid treatin agent and the mixture allowedto separate into an up-,per alkane layer and a lower acid layer containing. the selectivelyextractedcolor compounds. T

Theextracted phenyl alkanes next pass by way of valve-controlledoverflow line I 8| to thesulfonation stage. o

In the usual case, the, phenyl alkanes of this invention may flowdirectly to, the sulfonation stage through valve-controlled by-pass lineI83. As here shown, the fresh alkanefeed passes by way of inlet line I82together with reaction mixture into sulfonator 31. Thesulfonationreaction is extremely rapid and is well over complete at thetime of: mixing the fresh alkane with the reaction mixture. However,longer contact times are utilized and intimate dispersion effected toobtain substantially 100% sulionation and insure against the presence ofunsulionated residues which tend to cause undesirable color or odor. Acontact time of up to about two hours assures these results and isobtained. in the .embodiment of Fig. 4 by the circulation of thereaction mixture from the bottom of the sulfonator through outletconduit I85to pump I86. Fresh acid is introduced by way of inlet linevI84. This acid together with previously formed reaction neutralizer 4Iby way herein described yields'a mixture of sulionic acids in which thesulfonic acid group is directly attached to the benzene rin and thisring is in turn attached -to an alkane of polypropylene structurecorresponding in molecular weight to polyprcpylenesboiling within theranges herein previously described. These sulfonic acids, even afterpreliminary removal of entrained acid by gravity separation, containsome free; sulfuric acid. Thus, the sulfonation mixture flowing to ofinlet line I94 is a mix- I ture of sulfuric acid and sulfonic acidsmixture flows to the inlet side of said pump which serves not cnly toforce circulation of the mixture, but also to intimately contactthe acidand hydrocarbon components and facilitate complete sulfonation. Thereaction mixture being circulated next passes to cooler I81 where heatof reaction is removed and the temperature of sulfonation controlled bycirculating any suitable heat exchange fluid through the cooler asindicated. Fresh phenyl alkane then flows intothe reaction mixture atthe outlet of the cooler and continues in the circulation cycle throughfeed inlet I82 to sulfonator 31. 11 4 Reaction temperatureiriif thesuifonation zone is important and should be maintained sufiicient-'ly'high to effect complete sulfonation but not so high as to causecolor deterioration or undesirable side reactions. Exemplary operatingconditions are illustrated by sulfonation with 20% fuming sulfuric acidin an amount of about 200 pounds of acid for each 175 pounds of phenylalkane while maintaining the reaction temperature belowa maximum ofabout 136 F. and generally above about 90. F. with a residence time inthesulfonator under these conditions of about two hours'I j Thesulfonated phenyl alkane together with entrained acid is passed fromsulfonator 31 by way of outlet line 38 either directly tothe'neutralization stage as indicated by valve-controlled bypass I88 orto settler 39 by valve-controlled conduit I89. Water may be introducedinto the reaction mixture through line I 9| when desired and facilitatesseparation of the acid and the sulfonated oily layer into separatephases in's'ettler 39. Upon separation of thereaction mixture intoseparate phases, the lower sulfuric acid layer may be removed throughoutlet conduit. I92 and recycled through valve-controlled line I 9II- topump I86 when desired. In atypical operation, such as previouslydescribed, to'35 pounds of acids will be withdrawn as a lowerlayer insettler 39 for each 200 pounds of acid originally introduced insulfonator 37. Theremaining sulfonated' layer, when neutralized,will'yieldfa compositioncontaining about 60% of the'salt'lofsulfonatedphenyl aikanes and about 40 sodium sulfate.

In the neutralization it is preferred to introducethe sulfonic acidmixture slowly into a Vigorously stirred body of aqueous caustic sodasolution previously fed to the neutralizer through a line I96 in orderthat a morefluid solution will 7 form. Also, an excess of alkalidesirably should be present throughout the neutralization and until anend point of from about pH 7.0 to pH 8.5

- is reached. This procedure gives a superior product and preventslocaloverheating and color deterioration occasioned *by the reverseprocedure of addition of;caustlc to the sulfonic acid reaction mixture.If desired, alcohol also may be added to neutralizer 4I further toincrease fluidity of the reaction mixture and thereby promote effectivecontact between the reacting ingredients as well as better temperaturecontrol.

Temperature of reaction in the neutralizer is exceedingly importantsince it has been found that excessively high temperaturesofneutralizationinstigate color deterioration. This'is particularly trueif the free sulionic acids rather than sodium salts thereof aresubjected to high -temperatures and it is for this reason that an excessof caustic is maintained up to. theend point of the reaction whilesimultaneously maintaining temperature during neutralization below amaximumof about 130 F. and preferably no higher than about 120 F. Inorder to efl'ect this temperature control, the reaction'mixture iscontinuously circulated by way of'outlet conduit I91,

' rasodium pyrophosphate, sodium silicate, and the like. -Solublemagnesium salts in small amounts (for example i-5%) also may be added.Alkali metall'salts of high molecular weight carboxylic acids, such asthe sodium salt of carboxymethyl cellulose, Lha've'been found to enhancedetergency,

particularly on cotton fabrics.

The separation of acid layer is found further to 3 improve color andodorof inferiorproducts.

However, because of the high quality of the phenyl alkanes produced inaccordance with this invention, such a separation is usually unnecessaryunless the sulfate contentfof the sulfonate istobe reduced, and it isgenerally preferred to pass the sulfonated phenyl alkane together withits entrained acid directly to neutralizer 4|? In those instances wheresettler 39 is utilized to which-isparticularly adaptedto yield a strong,

further improve color or to yieldproduct of lower sulfate content, thesulfonated phenyl alka'neflows by way of valve-controlled outlet I93 toneutralizerfl. v I I.

'Sulfonator 3| under the reaction conditions should havev .Thesulfonate. compositions of this invention maybe'vproduced in the form ofa concentrated aqueous slurry which'may be sold as such but hollow,globular, spray-dried product. The productionof such a concentratedslurry, sufiicientiy fluid to be p'u'mpable atsuitable handlingtemperatures, for example, 70-130" F. and yet, which does'not'stratify;unduly during'handling or yield v inferior spray-dried globules'whichcollapse easily to form fines, ;requires a critical correlation ofproportions] of ingredients, A suitable slurry but no mdrethan about andpreferably from"*5 5 6 0% by 'weight based onthe total slurry.x'Thefsolids, content of such a slurry water content of at least 50% shouldcontain no more than from about to by weight of the sulfonate, theremainder being inorganic salt exemplified by sodium sulis utilized, and15-35 pounds of sulfuric acid is withdrawn. The remaining sulfonatelayer is then neutralized with about 300 pounds of 41% caustic sodawater solution and finished to a pH of about 7.5. The resulting mixturewill contain from about -65% water, and thesolids will consist of aboutneutralized sulionic acid and about 40% sodium sulfate. It usually willbe found desirable to build up the sodium sulfate content of this slurryto from 50 to by weight of the sodium sulfonate content thereof to avoidgelling. This may be done byintroducing additional sodium sulfatethrough valve-controlled line 202, and the sulfate so introduced may beobtained by means of neutralization of sulfuric acid from settler 39with alkali such as sodium carbonate or sodium hydroxide as shown at205.

The finished slurry is readily handled as a pumpable mixture and may bespray-dried to form hollow globular particles of 20 to 40 mesh which aresumciently strong to resist collapse or objectionable formation of finesduring packaging and distribution.

In those instances where it'may be desired for special reasons toproduce a. relatively pure sulfonate, the aqueous slurry withdrawn fromneutralizer ll may now from outlet conduit I91 by ferred, however, inmost instances to utilize the sulfonate-sulfate mixture as previouslydescribed.

Depending upon the final use of the product and the most desirablephysical form therefor, the aqueous slurry may be stored as such orconverted to a dried product in any suitable drier 42. It has been foundthat a flake product, such asis formed on a drum drier, and aspray-dried product are preferred physical forms. An exemplaryspray-dried product may be prepared in accordance with Lamont, U. S.Patent No. 1,652,900, issued December 13, 1927, to yield a preferredhollow, globular type substantially nondusting form found especiallydesirable for small package marketing in the household detergent Thesulfonate detergents herein disclosed possess surface-active propertiesand give marked effects in water at extremely low concentrations. Aslittle as one molecule in 40,000 imparts marked foaming properties andgood detergency even on grimy fabrics. One molecule of the detergent ofthis invention in a hundred thousand molecules of water is capable ofdecreasing the surface tension from 73 dynes per centimeter to 29 dynesper Unless otherwise indicated the following test data are on adetergent product containing about 60% sodium sulfate and having theforegoing properties. i

To illustrate more specifically the detergency properties of thecompounds and compositions herein disclosed, tests were run on heavilysoiled worsted at 110 F. in the Launder-O-Meter (test described in theOflicial Test Methods of American Association of Textile Chemists andColorists, published 1940).

The water had a hardness of 200 parts per million as calcium carbonateplus 100 parts per million as carbonate of magnesium. Four twentyminutewashes and two ten-minute rinses were given. The results expressed asper cent soil removal are given below.

Concentration Boil Removal 7 Per cent Per cent Similar tests on cottonhave shown that the detergent of this invention is excellent for thisfabric also and that it responds well to various types of builders. Forexample, in a test such as that above, but using a heavily-soiledfinelywoven (and hence diflicult to clean) cotton at a temperature of140 F., a high grade commercial soap at 0.2% concentration has adetergency rating of 100 whereas the detergent herein disclosed at thesame concentration has a detergency rating of 265. It is indicated alsothat in tests in hard water on cotton cloth soiled according to themethod given in U. 8. Navy Specification 51-8-47 (Int) Bureau of Ships,October 1, 1945, this detergent has synergistic action in conjunctionwith alkaline builders, such as trisodium phosphate.

Apparatus and procedure as described by Ross and Miles (Oil and Soap,May 1941, pp. 99-102) were used to check the height to which foam rosein a jacketed tube when 200 cc. fell in a fine stream down through adistance of centimeters. The test was run in 300 P. P. M. hard water and50 P. P. M. hard water with solutions and apparatus maintained at 110 F.

Weight Percent Concentration In 300 P. P. M. Water:

.0.20 205 In 50 P.

similar tests run by the method of Ross and Miles at F. with totalsolids held at a concentration of 0.2% while various ratios of thedetergent of this invention and alkalies, such as trisodium phosphate,were employed gave foa heights as stated. a

Foam height by Ross-Miles Test suljonate detergent and trisodiumphosphate 300 P. P. M.

hardness water [Total solids==2%] Sulfonate Trlsodium Foam DetergentPhosphate Height Per cent Per cent Millimeter:

One inch squares of 10 oz. cotton duck were observed'for the time inseconds required for them to wet and Sink in the detergent solutions ofvarying concentrations in distilled water, 1% sodium hydroxide and 5%sulfuric acid.

Wetting time oz. cotton duck] Distilled" 57 Sulfuric 17 Sodium Cmwnmm"Water Acid H ydroxide Graphical interpolations in' the above data givethe concentrations of the detergent of this inventionnecessary for, 25second wetting time as 0.28% in distilled water, 0.27% in 1% sodiumby-'- vdroxide, and 0.31% in 5% sulfuricacid.

Cotton wetting tests run by the Draves method were run at 25 C. indistilled water, 1% sulfuric acid and 1 sodium hydroxide. A three-gramhook was used.

Draves Sinking Time C ncentr tion Detergent o a Distilled 1% Sulfuric 1%Sodium Water Acid Hydroxide 0.00%; ...hours.. Over 24 0.05%. seconds 250300 167 0.10%- -.d0.. 25 40.5 29.9 0.257 ..-.do--. 5. 9 6. 5 8. 3 0.50%...do 3. 2 2. 9 5.1 0.75% 0... 2.8 2.5 4.5 1.00% -.d0' 2.4 2.2

The solubility of the detergent has been determined in distilled water,1% sulfuric acid, and 1% sodium hydroxide by measuring the minimumtemperature which gives a. clear solution for a given concentration.From these data the solubility at any desired temperature can bedeterfor wetting and sinking a standard skein of yarn I catcd asapproximately 2.3%.

28 At 68 F. the clear solubility of detergent in either distilled wateror 1% sulfuric acid is indi- Clear solubility in hard water wasdetermined by titrating the sulfonate detergent solutions withconcentrated hard water to a point where the turbidity just obscured themarkings on a 50 cc. graduated cylinder as observed through thesolution.

Maximum Water y Hardness for Concentration Clear Solution Detergent at68 F. in

p. p. in. CalciumCarbonate Per Cent i More concentrated solutions 01'the sulfonate detergent are capable of giving clear solutions in evenharder water.

- Though the sulfonate detergent by itself is solpropyl to hexyl benzenesulfonate. Dilution of these concentrates gives solutions usable atslightly lower temperatures.

At room temperature (25 C.) 10% isopropyl alcohol. will dissolve thesulfonate detergent to give 20% by weight in the solution. Isopropylalcohol in strengths from 7% up to 20% readily dissolves 15% ofv thesulfonate detergent at-room temperature. However, at 40 C.. 7.5% to12.5% isopropyl alcohol can dissolve 20% of the sulfonate of thisinvention.

Surface tension measurements at 25? C. run on Du Nuoy Tensiometer aregiven as well as int'erfacial tensions relative to a U. S. P. White Oilof 29.5 dynes per centimeter surface tension. Results are given forsolutions in 300 P. P. M. hard water as well as distilled water.

Con cggtras rl e Interracial Detergent (Dim Tensmn DISTILLED WATER Percent 300 P. P. M. HARD WATER An illustration of the stability of thisdetergent is given by the following test. Two per cent of the sulfonatedetergent dispersed in 10% sodium hydroxide was refluxed for 24- hoursat a temtested for foam height and wetting time.

Test Used Initial Final Foam (Ross-Miles) millimeters.. 228 230 WettingTime (10 oz. duck) -.seconds i 19 i 24 A similar test was run on asolution of 1% of detergent in 15% sulfuric acid, which was thenrefluxed for 24 hours. Samples from the beginning and end of the testwere diluted nine to one with water and checked for wetting time.

Test Used Initial Final The surface active properties of this detergentare not destroyed by boilingwith 10% caustic or 15% sulfuric acid.

A solution of 0.2% of the detergent of this invention in 0.25% sodiumhypochlorite was allowed to stand 80 hours. A check on the wetting timesof the solution at start and finish gave 18.2 sec. initially and 17.3sec. finally on 10 oz. cotton duck.

Further than this a 0.2% suspension of the detergent in 5.2% sodiumhypochlorite solution was analyzed at the beginning and end of a fouruntil it was no longer possible to see through the solution. The resultsare expressed as number of milligrams of metallic salt added to causeturbidlty.

Metallic salt: Mgs. to cause turbidity Aluminum sulfate 2 Bariumchloride 2 Calcium chloride 18 Copper sulfate- 67 Ferric sulfate. 4 Leadnitrate 3 1 Magnesium sulfate 46 Mercuric chloride 100 Nickel nitrate 35Zinc nitrate"; 43

The sulfonate compositions herein disclosed have a variety ofapplications in industry exemplified by the. following:

Quicker "break and easier rinsing on all goods merit applications incommercial laundries for the washing of woolensand fine fabrics as wellasfor grease and soil removal from high oil content washes such asoveralls and oil wiping cloths.

In the metal cleaning industry the sulfonates of this invention may beutilizedfor degreasing,

corrosion inhibiting or the like in acid pickling and clean rinsingsolution. i

I High sanitation in household dishwashing and of equipment andbuildings in dairy cleaning and food processing is obtainable with thesedetergents which are particularly adapted for washing V of fruits andvegetables prior toipacking or quickfreezing.

Use in liquid paint cleaners for bettergrime removal without effect onpaint luster, and utilization for automobile washing to give sparklingfinish'on weathered surfaces, further illustrate the attributes of thepresent sulfonated phenyl-- substituted alkanes. Likewise, thesecompounds may be utilized for W001 scouring, for penetration andevenness in dyeing and filling textiles, in pigment processing-to makewater colors and fillers for paper, cement, and water paints-as well asto improve wetting and spreading of insecticides or'herbicides and toincrease penetration thereof. These sulfonates also find application inblends with sodium bisulfate or with alkaline builders in industrialcleaning compounds. Again the surface activity of the sulfonatedcompounds of this invention adapts them for use in ore processing as acollector and frothing agent and in pulpand paper processing fordeflbrication, bleaching and rinsing.

The sulfonated phenyl alkane detergents of this invention may be used incombination or admixture with other wetting agents and detergents ofeither the anionicor non-ionic type. In general, from about four partsof sulfonated phenyl polypropylene detergent to one part of the additivewetting agent or detergent on the one hand, to from about one part ofsaid sulfonated phenyl polypropylene detergent to four parts of theadditive, may be utilized. Further, such admixtures may containinorganic salts, such as sodium sulfate, trisodium phosphate, sodiumsili-' 40 In the case of anionic additives the mixture usually willcontain sodium sulfate or the like in an amount of from about 40-80% byweight based on the entire detergent composition. Additive wettingagents and detergents of the above-mentioned anionic type, which may beutilized in combination with sulfonated phenyl polypropylene detergentsas disclosed, are exemplified by primaryalkyl sulfates, secondary alkylsulfates, sulfated glycerol esters, aliphatic sulfonates, sulfonatedesters or amides of fatty acids (Igepons), sulfonated or sulfatedpolyglycol ethers of alkyl phenols, mixtures of sulfonate-substitutedcompounds obtained by addition of nitrosyl chloride to an olefinfollowed by reaction with sodium sulfite, alkyl sulfoacetates, salts ofalkenyl succinic acids and salts of monoalkyl esters of alken ylsuccinic acids. Non-ionic types of wetting agents and detergentslikewise utilizable in combination with sulfonated phenyl polypropylenedetergents as previously disclosed are illustrated by polyglycol ethersof alkyl phenols, poly-glycol esters of fatty acids, alkyl polyglycolethers, polyglycol derivatives of alkyl amines, condensation anddetergents are characterized by a polar Non-ionic detergents arecharacterized by ether,

ester, amino and analogous polar groups.

. Examples: Lauryl sodium sulfate; cetyl sodium sulfate; poly propylenesodium sulfate; Keryl" sodium sulfate. (2) Sulfated esters e (a)Sulfaited diglycerides R-L-O-CH:

R-(|L|0- H Examples: Sulfatod monopalm oil, lard oil, ancLthe like.

(12) Sulfated mono-glycerides a-o-o-cm H: --0 ONa l Examples: Suliatedmonoand di glycerides from cocoanut oil, palm oil, lard oil, and thelike.

and di-glycerirles from cocoanut oil,

3) Sulfated ethers' 40 ta) sulfated glyceryldi-ethers Examples: 0 ctyl,lauryl, inonodi ethers oi glycerine: I, I lLsu tfonates' (1)Allrylsulfonates I Examples: R may be octyl, deoyl, oetyl, paraifln wax,polypropylene, .f-Ker'yl'j or other mineral oil aliphatic type radicals.v (gi'aikylhydrexy aromaticsulIonates 1 Exain' les: may be octyl decylcetyl,"wax pol r'o; pylene, Keryl or other mineral oil aliphatic type y?cleansing properties.

jf ous isomeric'cnand ;;.pre" sent-'therein. I a

I Obviouslymany modifications and :variatibfis "of the invention, ashereinbeforeset forth, may be made'without departing from the spirit'andI scope thereoflan'd only such limitations should be'imposed asaregindicatedin the appended v III Non-ionic time (1) Polyglycol ethersof alkyl' phenols Examples: R'is lauryl, cetyl, Kerylfl polypropylene,paramn wax etc and z is 2 to 20.

(2)' Polyglycol esters of aliphatic acids R-C,O(CH1-CH;O),CHz-CH'1OHExamples: R-(fi-Q may be laurlc, stearie, O I elc. palmitic ornaphthenic acid radicals a naz szm 20. l

3) Alkyl polygiycoi ethers it Examples: R E glyceryl, lauryl, cetyl,"Keryl, polypropylene, paraflln wax, etc.. and a: is 2 to 20.

(4) Polyg-lycol derivatives of alkyl amines Examples: R may be octyl,paraCn wax, etc, and I is 2 to (b) Dialkyl amine derivatives I I I If ti E 1 :R as 'b ,tl,l 1, tl,K 1," 1- prog' fia parag n watftj, attis 2$82K. y (5) V Alkyl polyalkylene polyamines R-N-cHrcHr-o L-cHr-cH=.-o11,cmxn H I j Examples: R may be ootyl, lauryl, cetyl, Keryrf'polypropylene, parailin wax, etc., and: is 2 to 20. p

Theforegoing disclosures relate to the utility of alkali metal salts ofthe phenyl sulfonic acid substituted polypropylene alkanes. II It is tobe understood *that other salts of these sulfonic acids have surfaceactivity and other useful properties. For example, the ammonium, calciumand magnesium salts thereof possess wetting and detergent properties.Additionally the free (unneutralized) sulfonic acids of phenyisubstituted polypropylene alkanes may be freed of entrained sulfuricacidbyany suitablemethod, such as alcoholicextraction to yield sulfonicacid compositions having useful surface active and l vIn thespecification and the appended claims the terms v tetramer" andffperitainer areused' alternatively to the terms 012" polymer fraction 1I and "C15" polymer fraction respectively. It is to be understood thatthe p0lymerization reaotion does not "proceed so smoothly or accuratelyas to yield onlyexact tetraor penta-multiples of the olefine feedbut'that the terms tetra'mer, or I 'fpentamer" as .used in thisspecification are meant to be desoriptivepf those hydrocarbons presentin the polymerproductf and ib oilin'g respectively "in the C12 andC ifaoleflne bbiling ranges which ranges embrace theboiling points o fTvari-Cnfpolymer hydrocarbons claims. I

This application is a continuation-in-part of 2%!3'1, cetyl, Keryl,polypropylene,

